Manufacture or treatment of products or articles having a basis of cellulose derivatives



This compoun Patented Apr. 14, 1936 I UNITED STATES MANUFACTURE OR TREATMENT OF PROD- UCTS OR ARTICLES CELLULOSE DERIVA HAVING A BASIS OF TIVES Henry Dreyfus, London, England No Drawing. Original application July Divided and this Serial No. 620,545. tion June 1'7, 1933, Seri Britain July 30, 1931 16 Claims.

This invention relates to the manufacture or treatment of products or articles made of or containing cellulose derivatives.

This application is a division of my application Serial No. 620,545 filed 1st July 1932.

The invention is based on the discovery that certain'cyclic compounds have a solvent or softening action upon cellulose derivatives and may be applied very widely in the arts in processes and products in which a solvent or softening action upon cellulose derivatives is desired. The cyclic compounds of the present invention are compounds containing a ring which consists of a keto group, an ether oxygen atom and four methylene or substituted methylene groups. These compounds will for convenience be termed oxanones. The simplest compound of the senes is tetra-hydropyrone I /CHr-CH2 o co GET-CH2 which will be hereinafter termed IA-oxanone.

d with its substitution derivatives constitute the most important solvents and softening agents of the present invention.

As previously indicated the invention contemplates processes and products utilizing the solvent or softening (including plasticizing) properties of'these compounds for cellulose deriva tives. 1.4-oxanone possesses very high solvent power for acetone-soluble cellulose acetate and -for other esters and ethers of cellulose including nitrocellulose. Substitution of the hydrogen atoms of the methylene groups in 1.4-oxanone tends to decrease somewhat the solvent power of the product except where the substituent groups themselves confer solvent or softening properties. Thus, for instance, alkylated, aralkylated or arylated 1.41-oxanones have in general less solvent power for acetone-soluble cellulose acetate than has the parent 1.4-oxanone. On the other hand 1.4-oxanone substituted in the methylene groups by polar groups, for instance carboxylic ester groups, has again high solvent power for cellulose acetate.

The present invention relates therefore to processes in which the solvent or softening power of the oxanones is employed in the production and treatment of artificial filaments, ribbons, films and the like comprising cellulose esters or ethers,

. and comprises quite broadly the treatment of the materials at any stage during or subsequent .to their formation. Thus, for example, the oxanones may be employed in media for the cotaining high concentrations 0 1, 1932, applicaal No. 676,338. In Great agulation of products spun by wet spinning processes from spinning solutions containing cellulose esters or ethers, or may be employed in subsequent treatment baths for such products. Again, the oxanones may be employed in processes for stretching, shrinking, improving the pliability, tenacity, or extension ofartificial filaments and the like, as well as in sizing, dyeing, printing, discharging, loading, mordanting, delustring and relustring artificial materials con- 10 taining esters or ethers of cellulose. I

As stated above, the oxanones may be employed in coagulating baths for the'wet spinning of cellulose derivatives, whether or not oxanones are present in the spinning solutions, and it is of 15 particular advantage for many purposes to employ relatively high concentrations of the oxanones in the coagulating baths. Moreover, after a wet spinning operation in which the oxanone is included in the spinning solution or in '20 the coagulating bath, or in which no oxanone is used at all, the filaments or other products may be treated in subsequent treatment baths containing oxanones. Wet spinning processes in which coagulating or after i solvents are employed are described in U. S. Patent No. 1,467,493 and U. S. applications Serial Nos. 402,785 filed 26th October, 1929, and 418,414 filed 3rd January, 1930. 30

In addition to being of value in the production of artificial filaments and other products containing cellulose esters and ethers by wet spinning processes as described above the solvents, softening agents or plasticizers of the-present invention 5 are also highly valuable for the treatment of already formed articles made of or containing cellulose derivatives, for example filaments, yarns, threads,'ribbons, films, fabrics and the like. Such treatments may have various objects. For ex- 40 ample the tendency of woven fabrics to slip or of warp or circular knitted fabrics to split or ladder may be diminished or eliminated by treatment with the oxanones of the present invention in the manner described in U. S. application Serial No. 152,516 filed 3rd December, 1926. The solvents may be used to improve the pliability or extension of filaments, threads and the like made of or containing cellulose derivatives, and in particular to improve the knotting properties of comparatively thick filaments orartificial horsehair. Such treatment with the oxanones is preferably effected without tension or only under alight tension so that the materials are able to shrink. Shrinking of the filaments, yarns and the like either to imv -treatment baths con- 25 i other products of cellulose acetate or other cellulose derivatives. In such an application the filaments or other products during or subsequent to softening with the oxanones or mixtures containing the same are subjected to a stretching treatment. The softening of the filaments or other products may be effected by treatment with the oxanones or solutions thereof, or the oxanones may be incorporated in the materials by incorporating them in the spinning solution and spinningundersuchconditions that theproportion of oxanone requisite to produce the desired degree of softening is retained in the filaments. Thus the required proportion may be incorporated in the spinning solution and the latter spun by dry spinning methods. The stretching treatment of the softened filaments or other products may be applied in a single operation and preferably gradually, or may be applied in a number of stages, preferably without intermediate elimination of the solvent as described in U. S. application Serial No. 402,785. From the point of view of producing regularity of stretch and'also for reasons of economy it is particularly advantageous to stretch the filaments or other products while they are in warp formation by applying the stretching force to the warp as a whole. Such a process is described in U. S. application Serial No. 602,844 filed 2nd April, 1932.

For the treatment of filaments, yarns and the like of cellulose derivatives, sizes may be made up containing the oxanones so as to effect a lubrication pf the yarns or other materials, particularly for facilitating textile operations, such as winding, winding and twisting, beaming and the like. Such sizes may be made up with or without suitable thickening agents, such as polymerized vinyl compounds, or oxidized linseed oil or other drying oils.

The oxanones are also of considerable value in processes for altering or modifying the optical characteristics of filaments, fabrics and the like containing cellulose esters or ethers, for example in relation to colour or lustre, and are of particular value .in processes involving the absorption of various liquid or solid materials by filaments, yarns, threads, fabrics and the like containing the cellulose esters or ethers. For example, such products may be treated with the oxanones during or before a treatment adapted to dye, print,

esses,'the acid wool and directcotton dyestuffs,

certainvat dyestuffs, pigments (white or coloured,)

for example titanium oxide, and certain discharges, for example the formaldehyde sulphoxylate discharges. Furthermore in printing and similar operations, it is customary to apply a steaming or ageing treatment to fix the dyestuff or other agent in the material. By incorporating the oxanones in the printing pastes or similar compositions the materials may be simply dried under such conditions as to volatilize the oxanone in order to effect fixation without having recourse to steaming or ageing. 1.4-oxanone and its lower homologues are particularly useful for this purpose. Again in the treatment of yarns, fabrics, etc. the oxanones of the present invention may be utilized to reluster fabrics or other materials containing cellulose acetate or other esters or ethers of cellulose which have been delustered by the action of moist steam or of hot aqueous media, and reference is made in this connection to U. S. Patent No. 1,808,098. Such relustering may be uniformly applied over the whole fabric or material, or may be local so as to produce an effect fabric. The oxanone may forinstance be printed with the aid of a suitable thickening agent on the delustered fabric and the whole dried to reluster the fabric in the printed portions. Dyestuffs, pigments, discharges or other effect materials may be included in the oxanone printing paste.

In the above applications of the oxanones of the present invention to products made of or containing cellulose acetate or other cellulose esters or ethers, the oxanones may be employed as such, particularly where they are liquids and their solvent power has been reduced by suitable substituent groups, as for instance alkyl groups. The oxanones may, of course, be mixed with other solvents, or, where their solvent power is too great, they may be mixed with suitable diluents. Thus, for example the oxanones may be employed in conjunction with other solvents and/or dilu- 'ents, for example acetone, methyl acetone, methyl olefine glycols, for instance the monomethyl and ethyl ethers of ethylene and propylene glycol and ethylene glycol mono-acetate and methyl glycol mono-acetate, methylene chloride, ethylene chloride, dichlorethylene, trichlorethylene, chloroform, methyl, ethyl or other alcohols, benzene, toluene, xylene or other aromatic, aliphatic or cyclo aliphatic hydrocarbons, and ethers, for instance iso-propyl ether. Furthermore, the oxanones may be employed in conjunction with relatively high boiling solvents or plasticizers which may themselves be oxanones, as for example 2.6- dimethyl-1.4-oxanone-3.fi-dicarboxylic acid dibutyl or di-iso-amyl ester, or may be other high boiling solvents or plasticizers, for example triacetin, diethyl phthalate, dibutyl phthalate, sulphonamides, for example alkylated xylene sulphonamides, sulphonanilides, tartrates, for instance dibutyl or di-iso-amyl tartrate, or diphenylol propane, triphenyl phosphate, tricresyl phosphate (the latter two preferably in conjunction with sulphonamides, tartrates or other highly compatible plasticizers), or other phenolic plasticizers. Again, the oxanones may be employed in conjunction with medium boiling solvents such as ethyl lactate, diacetone alcohol and tetrachlorethane. Moreover, mixtures of any of the above solvents, diluents and plasticizers may be employed inconjunction with the oxanones for the purposes of the present invention.

e As previously mentioned 1.4-oxanone itself is and either delustered or of a normal lustre is printed with the following printing paste:-

Grams Dyestuff or pigment 10-35 Diethylene glycol 60-75 Water 160 l.4=oxanone 200-500 Gum arable (1:1) 400-600 CoHa-?H CHCOH5 CuHr-CH CH CH-CuHg and CHFCHK C CH: OHs-C H. CHr-C C-CH8 The invention is particularly important in relation to the treatment of artificial silk, ribbons, films, fabrics and the like of cellulose acetate, but it may also be applied in the treatment of similar products of cellulose nitrate and also of cellulose formate, cellulose propionate, cellulose butyrate, cellulose nltro-acetate (of low nitrogen content) and other organic esters of cellulose or mixed esters, and. also ethyl or benzyl celluloses or other cellulose, ethers or mixed ethers or mixed ether-esters.

The following examples serve to illustrate the invention but are not-to be considered as limiting it in any way:-

- Example 1 A 25% solution of cellulose acetate in'acetone is extruded through spinning nozzles into a coagulating bath consisting of a 30-40% aqueous, alcoholic, or aqueous-alcoholic solution of 1.4- oxanone. The soft filaments after emergence from the coagulating bath are carried through a guide to a rotating roller having a peripheral speed of 50-70 metres per minute. The filaments may be drawn down to very fine deniers, After leaving the feed roller the excess oxanone is removed, as for example by washing it with a more dilute solution of oxanone, for instance a -15% solution, and the filaments are finally dried. In this example the spinning solution may contain 10% on the weight of the cellulose acetate of lA-oxanone.

Example 2 Filaments or yarns of cellulose, acetate in hank or other suitable form are soaked for about 2 minutes in a bath consisting of 30-40% aqueous,

' alcoholic, or aqueous-alcoholic solution of 1.4-

oxanone and are thereafter stretched to the desired degree, for example by more than 100% of A fabric consisting of cellulose acetate yarns cient time to cause the oxanone to evaporate and is then washed with warm water, soaped for a few minutes at 50 C. in a solution containing 2 grams of soap perv litre and finally rinsed. Where a delustered fabric has been used and the printing paste includes a dyestufi, the lustre of the printed areas is restored.

What I claim and desire to secure by Letters Patent is:-

1. In a process for the manufacture of filaments, yarns, threads, films, fabrics, and other. materials comprising organic derivatives of cellulose, the step of treating the materials with oxano nes.

2. In a process for the manufacture of filaments, yarns, threads, films, fabrics, and other materials comprising cellulose acetate, the step of treating the materials with oxanones.

3. In a process for the manufacture of filaments, yams, threads, films, fabrics, and other materials comprising cellulose acetate, the step of treating the materials with 1.4-oxanone.

4. Process for the manufacture of filaments,

yarns, films and the like, comprising extruding a solution containing an organic derivative of cellulose into a coagulating bath containing an oxanone.

5. Process for the manufacture of filaments, yarns, films and the like, comprising extruding a solution containing cellulose acetate into a coagulating bath containing 1.4-oxanone.

6. Process for the manufacture of filaments,

I yarns, films and the like, comprising extruding a solution containing cellulose acetate into a coagulating bath containing a high proportion of an oxanone.

'7. In a process for the manufacture of filaments, yarns, films or other products comprising organic derivatives of cellulose, the step of treating the materials after their formation with oxanones.

8. In a process for the manufacture of filaments, yarns, threads,'films, fabrics, or other materials comprising organic derivatives of cellulose, the step of softening the materials with the aid of oxanones,

9. Process for the manufacture of filaments, threads, yarns, andthe like comprising organic derivatives of cellulose, comprising softening the materials with the aid of an oxanone and subjecting them to a stretching treatment.

10. Process for the manufacture of filaments, threads, yarns, and the like comprising organic derivatives of cellulose, comprising softening a number of filaments, threads, yarns, and the like in warp formation with the aid of an oxa-' none and subjecting them to a stretching operation.

11. Process for the manufacture of filaments, threads, yarns, and the like comprising cellulose acetate, comprising softening the materials with the aid of 1.4-oxanone and subjecting them to a stretching operation.

12; Process for the manufacture of filaments, threads, yarns, and the like comprising organic derivatives of cellulose, comprising softening the materials with the aid of an ing the materials to shrink.

oxanone and allow- 13. In processes for colouring filaments, yarns,

threads, films, fabrics and othermaterials comprising organic derivatives of cellulose, the step of treating the materials with media comprising oxanones.

- 14. In processes for colouring filaments, yarns, threads, films, fabrics and other materials comprising cellulose acetate, the step of treating the materials with media comprising 1.4-oxanone.

15. In processes for modifying the lustre of filaments, yarns, threads, films, fabrics and other materials comprising organic derivatives of cellulose, the step of treating the materials with media comprising oxanones.

16, In processes for modifying the lustre of filaments, yarns, threads, films, fabrics and other materials comprising cellulose acetate, the step of treating the materials with media comprising l.4-oxanone.

HENRY DREYFUS. 20 

